EP1734066B1 - Polyrotaxan enthaltendes polymermaterial und herstellungsverfahren dafür - Google Patents

Polyrotaxan enthaltendes polymermaterial und herstellungsverfahren dafür Download PDF

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EP1734066B1
EP1734066B1 EP05727602.4A EP05727602A EP1734066B1 EP 1734066 B1 EP1734066 B1 EP 1734066B1 EP 05727602 A EP05727602 A EP 05727602A EP 1734066 B1 EP1734066 B1 EP 1734066B1
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polyrotaxane
polymer
molecule
cyclic
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EP1734066A1 (de
EP1734066A4 (de
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Kohzo c/o The University of Tokyo ITO
Masatoshi c/o The University of Tokyo KIDOWAKI
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University of Tokyo NUC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/007—Polyrotaxanes; Polycatenanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B01J20/267—Cross-linked polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G85/00—General processes for preparing compounds provided for in this subclass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/16—Cyclodextrin; Derivatives thereof

Definitions

  • the present invention relates to a material comprising polyrotaxane, and a method for producing the material.
  • Patent Document 1 discloses a crosslinked polyrotaxane, which is formed by crosslinking polyrotaxanes, each of which is comprised of pseudopolyrotaxane, which comprises a linear molecule (axis) and cyclic molecules (rota) in which the linear molecule is included in cavities of cyclic molecules in a skewered manner, and capping groups, each of which locates at each end of the pseudopolyrotaxane (each end of the linear molecule) in order to prevent the dissociation of the cyclic molecules.
  • the crosslinked polyrotaxane has viscoelasticity generated by the movement of a cyclic molecule. Thus, even if strain is applied to the crosslinked polyrotaxane, the strain is dispersed uniformly in the cross linked polyrotaxane by this action. Therefore, crack or scratch is not generated, differing from the crosslinked polymer.
  • Patent Document 2 describes polyrotaxanes, which are bound to each other through the cyclic molecule in the polyrotaxane, for use as electrolyte components.
  • Patent Document 3 describes a compound comprising a first and a second polyrotaxane, the polyrotaxanes being crosslinked by linking through the first cyclic molecules and the second cyclic molecules by a chemical bonding.
  • Patent Document 4 describes a crosslinked polyrotaxane, wherein at least two molecules of polyrotaxane are crosslinked with each other through physical bonding. The cyclodextrins aggregate on the same linear molecule and between polyrotaxane molecules.
  • Patent Document 5 describes at least one hydroxyl group of at least one cyclodextrin molecule in each of the at least two molecules of polyrotaxane is involved in crosslinking.
  • Patent Document 6 describes an absorbent polymer, which incorporates cyclodextrins and/or cyclodextrin derivatives, which is covalently and/or ionically bound therein.
  • Scientific Publication 1 describes polyrotaxane, in which ⁇ -Cyclodextrin are threaded onto a PEG chain, is later acetylated using acetic anhydride.
  • Scientific Publication 2 describes polyrotaxanes in which ⁇ -Cyclodextrins are threaded onto poly(ethylene glycol)-b-poly(propylene glycol)-b-poly(ethylene glycol)(PEG-b-PPG-b-PEG) triblock copolymers (pluronic).
  • Patent Document 7 describes an aminated polyrotaxane, in which at least some of hydroxy groups in the cyclodextrin structure are each substituted with a substituent having an amino group.
  • Scientific Publication 3 describes a preparation of modified polyurethanes by blending sulfonated polyrotaxanes (and physically bonding through PPG) with polyurethane solution. The sulfonated polyrotaxanes are obtained by threading sulfonated ⁇ -Cyclodextrins onto the PEG segments in a PEG-b-PPG-b-PEG triblock copolymer.
  • Scientific Publication 4 describes synthesis of a polyrotaxane consisting of ⁇ -Cyclodextrins and poly(ethyleneglycol) . Carboxyethylester-groups and taurine are successively conjugated with a polyrotaxane, and the formed taurine- Carboxyethylester- polyrotaxane polymer is used as an anticoagulant agent.
  • Scientific Publication 5 describes synthesis of maltose-polyrotaxane conjugates by a condensation reaction between b-maltosylamine and carboxyethylester-polyrotaxanes to enhance binding with protein.
  • An object of the present invention is to solve the problem described above.
  • an object of the present invention is to provide a material having a property of a crosslinked polymer together with a property of crosslinked polyrotaxane, and a method of producing the material.
  • an object of the present invention is to provide a material having a property of a crosslinked polymer together with stretchability or viscoelasticity, and a method of producing the material.
  • the present inventors have found that, by adopting a material comprising polyrotaxane and polymer, in which the polyrotaxane is bound to a part or all of the polymer through a cyclic molecule(s) of the polyrotaxane, the object can be attained.
  • the present inventors have found following inventions.
  • the present invention can provide a material having a property of a crosslinked polymer together with a property of crosslinkedpolyrotaxane, and a method of producing the material.
  • the present invention can provide a material having a property of a crosslinked polymer together with stretchability or viscoelasticity, and a method of producing the material.
  • the present invention provides a material comprising polyrotaxane and polymer.
  • polyrotaxane comprises a cyclic molecule, a linear molecule which is included in cavities of the cyclic molecules in a skewered manner, and a capping group which is located at each end of the linear molecule to prevent the dissociation of the cyclic molecules.
  • the material of the present invention is characterized in that at least a part of the polyrotaxane and the polymer is bound to each other through the cyclic molecule.
  • the material of the present invention having the constitution provides an action described below:
  • the cyclic molecule can move along the linear molecule.
  • force tension and/or stress
  • the material is capable of expansion and contraction by the movement of the cyclic molecule.
  • Fig. 1 shows a schematic view of a material 1 of the present invention.
  • the material 1 of the present invention comprises a polymer 3 and polyrotaxane 5.
  • the polyrotaxane 5 has a linear molecule 6, a cyclic molecule 7 and a capping group 8.
  • the polymer 3 and polymer 3' and the polyrotaxane 5 are bound through the cyclic molecule 7.
  • stress of deformation along an arrow direction is loaded on the material 1 as shown in Fig. 1(a)
  • the material 1 can adopt a configuration as shown in Fig. 1(b) .
  • the polyrotaxane and the polymer are bound or crosslinked.
  • Polymers may be mutually crosslinked or, polyrotaxanes may be mutually crosslinked.
  • the present invention can provide i) a material in which the polyrotaxane and the polymer are bound or crosslinked, and polymers are crosslinked and polyrotaxanes are crosslinked; ii) a material in which the polyrotaxane and the polymer are bound or crosslinked, and the polyrotaxanes are crosslinked, while polymers are not crosslinked; iii) a material in which the polyrotaxane and the polymer are bound or crosslinked, and the polymers are crosslinked, while the polyrotaxanes are not crosslinked; and iv) a material in which the polyrotaxane and the polymer are bound or crosslinked, while polymers are not crosslinked and polyrotaxanes are not crosslinked.
  • a polymer forms
  • polyrotaxane in a material according to the present invention can provide expansion and contraction of the material as described above. Accordingly, polyrotaxane may be present in the material according to the present invention.
  • the amount of polyrotaxane in a material depends on a nature required for the material. For example, the weight ratio of the polyrotaxane to the polymer ((polyrotaxane) / (polymer)) may be 1/1000 or more, namely, polyrotaxane is present in a proportion of 1 or more based on 1000 of a polymer.
  • At least a part of the polymers in a material according to the present invention may be physically and/or chemically crosslinked.
  • the polymer in a material according to the present invention may have on a backbone chain or side chain at least one selected from the group consisting of a -OH group, a -NH 2 group, a -COOH group, an epoxy group, a vinyl group, a thiol group and a photo-crosslinkable group.
  • the photo-crosslinkable group may include, but are not limited to, cinnamic acid, coumarin, chalcone, anthracene, styrylpyridine, styrylpyridinium salt, styrylquinolium salt and the like.
  • the polymer in the present invention may be a homopolymer or copolymer. Two or more polymers may be present. In a case where two or more polymers are present, at least one polymer may be bound to polyrotaxane through a cyclic molecule. In a case where the polymer of a material according to the present invention is a copolymer, it may be composed of two, or three or more monomers. In the case of a copolymer, the copolymer may be one of a block copolymer, alternating copolymer, random copolymer, graft copolymer and the like.
  • polymer may include, but not limited to, polyvinyl alcohol, polyvinylpyrrolidone, poly(meth)acrylic acid, cellulose-based resins (carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and the like), polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl acetal-based resins, polyvinyl methyl ether, polyamine, polyethyleneimine, casein, gelatin, starch and the like and/or copolymers thereof, polyolefin-based resins such as polyethylene, polypropylene, and copolymer resins with other olefinic monomers, polyester resins, polyvinyl chloride resins, polystyrene-based resins such as polystyrene, acrylonitrile-styrene copolymer resin and the like, acrylic resins such as polymethyl methacrylate, copolymer of (meth)acrylate, acrylonitrile
  • the derivatives may contain the above-described group, i.e., at least one selected from the group consisting of a -OH group, a -NH 2 group, a -COOH group, an epoxy group, a vinyl group, a thiol group and a photo-crosslinkable group.
  • the linear molecule of polyrotaxane in a material according to the present invention may include polyvinyl alcohol, polyvinylpyrrolidone, poly(meth)acrylic acid, cellulose-based resins (carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and the like), polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl acetal-based resins, polyvinyl methyl ether, polyamine, polyethyleneimine, casein, gelatin, starch and the like and/or copolymers thereof, polyolefin-based resins such as polyethylene, polypropylene, and copolymer resins with other olefinic monomers, polyester resins, polyvinyl chloride resins, polystyrene-based resins such as polystyrene, acrylonitrile-styrene copolymer resin and the like, acrylic resins such as polymethyl methacrylate, copolymer of (me
  • a molecular weight of the linear molecule according to the present invention may be 10,000 or more, preferably 20,000 or more, more preferably 35,000 or more.
  • the capping group of the polyrotaxane in the material according to the present invention is not limited, as long as the group has an action of preventing dissociation of a cyclic molecule from a linear molecule.
  • the capping group may be selected from the group consisting of dinitrophenyl groups; cyclodextrins; adamantane groups; trityl groups; fluoresceins; pyrenes; substituted benzenes (example of the substituent may include, but are not limited to, alkyl, alkyloxy, hydroxy, halogen, cyano, sulfonyl, carboxyl, amino, phenyl and the like.
  • the substituent may be single or plural.); polycyclic aromatics which may be substituted (examples of the substituent may include, but are not limited to, those described above.
  • the substituent maybe single or plural.) ; and steroids.
  • the capping group may be selected from the group consisting of dinitrophenyl groups; cyclodextrins; adamantane groups; trityl groups; fluoresceins; and pyrenes, more preferably adamantane groups; or trityl groups.
  • the cyclic molecule in the polyrotaxane according to the present invention may comprise at least one selected from the group consisting of a -OH group, a -NH 2 group, a -COOH group, an epoxy group, a vinyl group, a thiol group, and a photo-crosslinkable group.
  • the photo-crosslinkable group may include, but are not limited to, cinnamic acid, coumarin, chalcone, anthracene, styrylpyridine, styrylpyridinium salt, styrylquinolium salt and the like.
  • the cyclic molecule may be a cyclodextrin molecule which may be substituted.
  • the cyclodextrin may be selected from the group consisting of ⁇ -cyclodextrin, ⁇ -cyclodextrin and ⁇ -cyclodextrin, and derivatives thereof.
  • At least a part of a cyclic molecule in a polyrotaxane is bound to at least a part of a polymer as described above.
  • a group carried on the cyclic molecule for example, a -OH group, -NH 2 group, -COOH group, epoxy group, vinyl group, thiol group, photo-crosslinkable group or the like may be bound to a group carried on the backbone chain and/or side chain of the polymer, for example, a -OH group, -NH 2 group, -COOH group, epoxygroup, vinyl group, thiol group, photo-crosslinkablegroup or the like, via a chemical reaction.
  • the cyclic molecule may be a cyclodextrin molecule, and the linear molecule may be polyethylene glycol.
  • the linear molecule may have the cyclic molecules included in a skewered manner at an amount of 0.001 to 0.6, preferably 0.01 to 0.5, and more preferably 0.05 to 0.4 of a maximum inclusion amount, which is defined as an amount at which the cyclic molecules can be included at maximum when the linear molecule has the cyclic molecules included in a skeweredmanner, and the amount at maximum is normalized to be 1.
  • the maximum inclusion amount of a cyclic molecule can be determined depending on the length of a linear molecule and the thickness of a cyclic molecule .
  • the maximum inclusion amount is measured empirically (see, Macromolecules 1993, 26, 5698-5703 , whole contents of which is incorporated herein).
  • the polyrotaxane and the polymer may be chemically bound to each other by a crosslinking agent.
  • the crosslinking agent may have a molecular weight of less than 2,000, preferably less than 1, 000, more preferably less than 600, and most preferably less than 400.
  • the crosslinking agent may be selected from the group consisting of cyanuric chloride, trimesoyl chloride, terephthaloyl chloride, epichlorohydrin, dibromobenzene, glutaraldehyde, phenylene diisocyanate, tolylenediisocyanate, divinyl sulfone, 1,1'-carbonyldiimidazole and alkoxysilanes.
  • the material of the present invention can provide stretchability owing to the presence of polyrotaxane. As described above, stretchability depends on the amount of polyrotaxane, the inclusion amount described above, and the like, and it is preferable to control these amounts depending on a property required for the material.
  • the material according to the present invention can be applied to a polymer material required to have stretchability.
  • the polymer material may include, but are not limited to, optical materials, contact lenses, biomaterials, medical materials, tire materials, application agents, adhesives and the like; andenvironment-relatedmaterials, livingwares, civil engineering and construction materials, battery-related materials, foods, health materials, sports equipment and materials thereof, cloth and fashion materials, fibers, toy and entertainment materials, art-related materials, automobile-related materials, and the like.
  • Examples of the material may include, but are not limited to, the following materials.
  • examples of the application range of the material according to the present invention may include rubber band, packing material, agar medium, clothing fabric, shoe sole of sport shoes and the like, cushioning material or impulse absorbing material of helmet, protector and the like, bumper of automobile and various apparatuses, toy, coating material for friction part of apparatus (for example, coating material for sliding part or housing of pump), adhesive, sealing material for tight seal, dehumidification agent or dew removing material, filler for bed mat analogous to water bed, material for special effect photograph or material for miniature model, optical material such as material for soft contact lens (particularly, material for soft contact lens having high moisture content and/or excellent strength), material for tire, gel for electrophoresis, novel foodstuff pursuant to gum and the like, gum for dog, biomaterials including biocompatible materials such as artificial cornea, artificial crystalline lens, artificial vitreous body, artificial skin, artificial muscle, artificial joint, artificial cartilage and the like and material for breast enlargement and the like, medical materials used for outside of the body such as wet dressing material, wound covering material, medical
  • One embodiment of the method of producing the material according to the present invention comprises a) a step of mixing polyrotaxane comprising a cyclic molecule, a linear molecule which is included in cavities of the cyclic molecule in a skewered manner, and a capping group which is located at each end of the linear molecule to prevent the dissociation of the cyclic molecule, with a polymer; b) a step of physically and/or chemically crosslinking at least a part of the polymer, and c) a step of binding the at least a part of the polymer and polyrotaxane through the cyclic molecule.
  • the at least a part of the polymer may be chemically crosslinked.
  • the chemical crosslinking can be carried out, for example, using a crosslinking agent.
  • the crosslinking agent may include, but not limited to, the above-mentioned agents.
  • the step c) may be carried out before or after the step b).
  • the step b) and the step c) may be carried out at the substantially same time.
  • the mixing step a) may be carried out without solvent or in a solvent, depending on the polymer to be used.
  • the solvent may include, but are not limited to, water, toluene, xylene, benzene, anisol, cyclohexanone, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, methyl ethyl ketone, chloroform, dichloromethane, carbon tetrachloride, hexafluoroisopropyl alcohol, tetrahydrofuran, dioxane, acetone, ethyl acetate, dimethyl sulfoxide, acetonitrile and the like.
  • the crosslinking step b) may be carried out under polymer crosslinking conditions conventionally known. Examples thereof may include, but not limited to, the following conditions.
  • a cross linking reaction can be generated by heating or in the presence of active hydrogen such as in amine or acid anhydride. Further, a crosslinking reaction can be generated also by irradiation with light in the presence of a photo-acid generator or photo-base generator.
  • a crosslinking reaction can be generated by heating or irradiation with light in the presence of heat or photo-radical generator.
  • a crosslinking reaction can be generated by heating or irradiation with light.
  • a crosslinking reaction can be generated in the presence of poly-substituted isocyanates, carbodiimides, triazines or silanes.
  • a crosslinking reaction can also be generated by irradiation with electron beam.
  • the binding step c) may be carried out by a chemical reaction of a group carried on the polymer on its main chain and/or side chain, for example, a -OH group, -NH 2 group, -COOH group, epoxy group, vinyl group, thiol group, photo-crosslinkable group or the like with a group carried on the cyclic molecule, for example, a -OH group, -NH 2 group, -COOH group, epoxy group, vinyl group, thiol group, photo-crosslinkable group or the like.
  • the conditions for the binding step c) depend on the group carried on the polymer, the group carried on the cyclic molecule, and the like.
  • the conditions for the binding step may use, but not limited to, for example, the above-described crosslinking conditions.
  • the material according to the present invention can also be produced by the following production methods.
  • One embodiment of the method of producing the material according to the present invention comprises a) a step of mixing polyrotaxane comprising a cyclic molecule, a linear molecule which is included in cavities of the cyclic molecules in a skewered manner, and a capping group which is located at each end of the linear molecule to prevent the dissociation of the cyclic molecule, with a monomer constituting a polymer; b) a step of polymerizing the monomer to form a polymer, c) a step of physically and/or chemically crosslinking at least a part of the polymer, and d) a step of binding at least a part of the polymer and the polyrotaxane through the cyclic molecule.
  • the polymer may be chemically crosslinked.
  • the chemical crosslinking can be carried out, for example, using a crosslinking agent.
  • the crosslinking agent may include, but not limited to, the above-mentioned agents.
  • the steps b) and c) may be carried out at the substantially same time.
  • the steps c) and d) maybe carried out at the substantially same time. Further, the steps b), c) and d) may also be carried out at the substantially same time.
  • step d) may also be carried out before or after the step c).
  • the conditions for the step of polymerizing a monomer to form a polymer depend on the monomer to be used, and the like. As these conditions, conventionally known conditions can be used.
  • polyrotaxane polymer, cyclic molecule, linear molecule, capping group and the like to be used in the production method of the present invention
  • the same compounds as described above can be used.
  • the monomer constituting a polymer depends on the polymer, but is not particularly limited, as long as it can form the polymer.
  • the reaction was quenched by adding ethanol with an amount of up to 5 ml.
  • Ingredients other than inorganic salts were extracted with 50 ml of methylene chloride three times, and methylene chloride was removed with an evaporator.
  • the residue was dissolved in 250 ml of hot ethanol, and allowed to stand in a freezer at -4°C overnight to precipitate a PEG-carboxylic acid, in which each end of the PEG was substituted with carboxylic acid (-COOH).
  • the precipitated PEG-carboxylic acid was collected by centrifugation.
  • the collected PEG-carboxylic acid was subjected to the procedure consisting of dissolving in hot ethanol, precipitating and centrifuging, for several times, and finally dried in vacuum, to give a purified PEG-carboxylic acid. Yield was 95% or more. A degree of carboxylation was 95% or more.
  • Polyvinyl alcohol (hereinafter may be abbreviated as "PVA", degree of polymerization: 2,000) was dissolved in a 0.03N NaOH aqueous solution, to prepare a 1.0 ml of a 5 wt % solution.
  • PVA polyvinyl alcohol
  • PVA degree of polymerization: 2,000
  • Viscoelastic curves of the gelated bodies A-1 and A-2 were measured, to obtain results shown in Table 1 and Fig. 2 .
  • Table 1 and Fig. 2 show that the gelated body A-1 as the material according to the present invention was improved in extension ratio, owing to the presence of methylated polyrotaxane.
  • Table 1. Viscoelastic characteristics of gelated bodies A-1 and A-2 Gelated body Extension ratio (%) Maximum stress (kPa) Stiffness (kPa) A-1 320 35 12 A-2 149 25 20
  • PVA degree of polymerization: 2,000
  • methylated polyrotaxane Mw PEG : 500,000; degree of methylation: 30 %; degree of inclusion: 29%)
  • Mw PEG 500,000; degree of methylation: 30 %; degree of inclusion: 29%)
  • Mw PEG 500,000; degree of methylation: 30 %; degree of inclusion: 29%)
  • To 1.0 ml of the PVA solution was added 3 mg of the methylated polyrotaxane solution, and dissolved.
  • PVA degree of polymerization: 2,000
  • a 0.03N NaOH aqueous solution was dissolved in a 0.03N NaOH aqueous solution, to prepare 1.0 ml of a 5 wt % solution, and cooled at 5°C.
  • To the solution was added 10 ⁇ L of DVS, and then allowed to stand at temperature of 5°C for 20 hours, to obtain a gelated body A-4 of PVA.
  • Viscoelastic curves of the gelated bodies A-3 and A-4 were measured, to obtain results shown in Table 2 and Fig. 3 .
  • Table 2 and Fig. 3 show that the gelated body A-3 as the material according to the present invention was improved in extension ratio, owing to the presence of methylated polyrotaxane.
  • Table 2. Viscoelastic characteristics of gelated bodies A-3 and A-4 Gelated body Extension ratio (%) Maximum stress (kPa) Stiffness (kPa) A-3 334 3.3 0.8 A-4 291 6.6 2.3
  • a polyrotaxane was prepared in a manner similar to Example 1.
  • PVA degree of polymerization: 500
  • a 1NNaOH aqueous solution to prepare 1.0 ml of a 5 wt % PVA solution.
  • the hydroxypropylated polyrotaxane Mw PEG : 500,000; degree of hydroxypropylation: 35 %; degree of inclusion: 29%) was dissolved in a 1N NaOH aqueous solution, to prepare a 5 wt % hydroxypropylated polyrotaxane solution.
  • To 1.0 ml of the PVA solution was added 3 mg of the hydroxypropylated polyrotaxane solution, and dissolved.
  • Polyacrylic acid (hereinafter maybe abbreviated as "PAA", average molecular weight: 25,000) was dissolved in a 1N NaOH aqueous solution, to prepare 1.0 ml of a 15 wt % PAA solution.
  • PAA Polyacrylic acid
  • a polyrotaxane prepared in a manner similar to Example 1 Mw PEG : 35,000; degree of inclusion: 29%) was dissolved in a 1N NaOH aqueous solution, to prepare a 15 wt % polyrotaxane solution.
  • To 1.0 ml of the PAA solution was added 50 ⁇ L of the polyrotaxane solution, and mixed.
  • PAA average molecular weight: 25,000
  • a methylated polyrotaxane prepared in a manner similar to Example 1 (Mw PEG : 35,000; degree of methylation: 30 %; degree of inclusion: 29%) was dissolved in a 1N NaOH aqueous solution, to prepare a 15 wt % methylated polyrotaxane solution.
  • To 1.0 ml of the PAA solution was added 20 ⁇ L of the methylated polyrotaxane solution, and mixed.
  • PAA average molecular weight: 25,000
  • a hydroxypropylated polyrotaxane prepared in a manner similar to Example 4 (Mw PEG : 500,000; degree of hydroxypropylation: 35 %; degree of inclusion: 29%) was dissolved in a 1N NaOH aqueous solution, to prepare a 10 wt % hydroxypropylated polyrotaxane solution.
  • To 1.0 ml of the PAA solution was added 10 ⁇ L of the hydroxypropylated polyrotaxane solution, and mixed.
  • Collagen was dissolved in a 0.03N NaOH aqueous solution, to prepare 1.0 ml of a 2 wt % collagen solution.
  • a methylated polyrotaxane prepared in a manner similar to Example 1 (Mw PEG : 35,000; degree of methylation: 30 %; degree of inclusion: 29%) was dissolved in a 0.03N NaOH aqueous solution, to prepare a 2 wt % methylated polyrotaxane solution.
  • To 0.5 ml of the collagen solution was added 0.5 ml of the methylated polyrotaxane solution, and mixed.
  • Collagen was dissolved in a 0.03N NaOH aqueous solution, to prepare 1.0 ml of a 2 wt % collagen solution.
  • a hydroxypropylated polyrotaxane prepared in a manner similar to Example 4 (Mw PEG : 500,000; degree of hydroxypropylation: 35 %; degree of inclusion: 29%) was dissolved in a 0.03N NaOH aqueous solution, to prepare a 2 wt % hydroxypropylated polyrotaxane solution.
  • To 1 ml of the collagen solution was added 25 ⁇ L of the hydroxypropylated polyrotaxane solution, and mixed.
  • Collagen was dissolved in a 0.03N NaOH aqueous solution, to prepare 1.0 ml of a 2 wt% collagen solution. To the solution was added 10 ⁇ L of DVS, and then allowed to stand at temperature of 25°C for 20 hours, to obtain a gelated body of collagen.
  • the resulting gelated body was very fragile as compared with the gelated bodies of Examples 8 and 9, and was broken when touched with a hand. On the other hand, the gelated bodies of Examples 8 and 9 had elasticity and were not broken easily by touch. This teaches that the strength of the gelated body was improved by the presence of polyrotaxane.
  • HEC Hydroxyethyl cellulose
  • a methylated polyrotaxane prepared in a manner similar to Example 1 Mw PEG : 35,000; degree of methylation: 30 %; degree of inclusion: 29%) was dissolved in a 0.03N NaOH aqueous solution, to prepare a 5 wt % methylated polyrotaxane solution.
  • To 1 ml of the HEC solution was added 0.1 ml of the methylated polyrotaxane solution, and mixed.
  • Hydroxypropyl cellulose (abbreviated as "HPC") was dissolved in a 0.03N NaOH aqueous solution, to prepare 1.0 ml of a 5 wt % HPC solution.
  • HPC Hydroxypropyl cellulose
  • a hydroxypropylated polyrotaxane prepared in a manner similar to Example 4 Mw PEG : 500,000; degree of hydroxypropylation: 35 %; degree of inclusion: 29%) was dissolved in a 0.03N NaOH aqueous solution, to prepare a 5 wt % hydroxypropylated polyrotaxane solution.
  • To 1 ml of the HPC solution was added 10 ⁇ L of the hydroxypropylated polyrotaxane solution, and mixed.
  • a hydroxypropylated polyrotaxane was prepared in a manner similar to Example 3.
  • MAPVA methacryloylated polyvinyl alcohol
  • Mw PEG methacryloylated polyrotaxane
  • PAA average molecular weight: 25,000
  • Mw PEG methylated polyrotaxane
  • To the resulting solution were added 20 mg of N-ethyl-N'-(3-dimethylaminopropyl)carbodiimide and 20 ⁇ L of diisopropylethylamine, and the mixture was left at room temperature for 5 hours, to obtain a mixed gelated body including crosslinking of PAA and polyrotaxane via an ester bond (PAA:methylated polyrotaxane (weight ratio) 1:1).

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Claims (28)

  1. Material umfassend ein Polyrotaxan und ein Polymer, wobei das Polyrotaxan ein zyklisches Molekül, ein lineares Molekül, das in den Kavitäten des darauf aufgereihten zyklischen Moleküls (Moleküle) eingeschlossen ist, und Endgruppen umfasst, die zur Verhinderung der Dissoziation des zyklischen Moleküls (Moleküle) jeweils an den Enden des linearen Moleküls angeordnet sind, und wobei ein Teil des Polyrotaxans und das Polymer über das zyklische Molekül miteinander verbunden sind durch eine auf dem zyklischen Molekül befindlichen Gruppe, die an eine auf dem Rückgrat und/oder einer Seitenkette des Polymers befindlichen Gruppe gebunden ist.
  2. Material nach Anspruch 1, wobei das Gewichtsverhältnis des Polyrotaxans zu dem Polymer (Polyrotaxan / Polymer) mindestens 1/1000 beträgt.
  3. Material nach Anspruch 1 oder 2, wobei eine Rückgratkette oder eine Seitenkette des Polymers wenigstens eine Gruppe aufweist, die unter einer OH-Gruppe, einer NH2-Gruppe, einer COOH-Gruppe, einer Epoxygruppe, einer Vinylgruppe, einer Thiolgruppe und einer photovernetzbaren Gruppe ausgewählt ist.
  4. Material nach einem der Ansprüche 1 bis 3, wobei das lineare Molekül unter Polyethylenglycol, Polyisopren, Polyisobutylen, Polybutadien, Polypropylenglycol, Polytetrahydrofuran, Polydimethylsiloxan, Polyethylen und Polypropylen ausgewählt ist.
  5. Material nach einem der Ansprüche 1 bis 4, wobei das lineare Molekül ein Molekulargewicht von mindestens 10.000 hat.
  6. Material nach einem der Ansprüche 1 bis 5, wobei die Endgruppe unter Dinitrophenylgruppen, Cyclodextrinen, Adamantangruppen, Tritylgruppen, Fluoresceinen, Pyrenen, substituierten Benzolen, unsubstituierten und substituierten polycyclischen Aromaten und Steroiden ausgewählt ist.
  7. Material nach einem der Ansprüche 1 bis 6, wobei das zyklische Molekül wenigstens eine Gruppe aufweist, die unter einer OH-Gruppe, einer NH2-Gruppe, einer COOH-Gruppe, einer Epoxygruppe, einer Vinylgruppe, einer Thiolgruppe und einer photovernetzbaren Gruppe ausgewählt ist.
  8. Material nach einem der Ansprüche 1 bis 7, wobei das zyklische Molekül ein unsubstituiertes oder substituiertes Cyclodextrinmolekül ist.
  9. Material nach einem der Ansprüche 1 bis 7, wobei das zyklische Molekül ein unsubstituiertes oder substituiertes Cyclodextrinmolekül ist, das unter α-Cyclodextrin, β-Cyclodextrin und γ-Cyclodextrin und deren Derivaten ausgewählt ist.
  10. Material nach einem der Ansprüche 1 bis 9, wobei das zyklische Molekül ein unsubstituiertes oder substituiertes α-Cyclodextrin ist und das lineare Molekül Polyethylenglycol ist.
  11. Material nach einem der Ansprüche 8 bis 10, wobei ein Substituent des substituierten Cyclodextrinmoleküls oder des substituierten α-Cyclodextrinmoleküls mindestens ein Substituent ist, der unter einer Methylgruppe, einer Hydroxylgruppe und einer Gruppe, die eine (Meth)acryloylgruppe aufweist, ausgewählt ist.
  12. Material nach einem der Ansprüche 1 bis 11, wobei das lineare Molekül das darauf aufgereihte zyklische Molekül (Moleküle) in einer Menge einschließt, die 0,001 bis 0,6 der maximalen Einschlussmenge beträgt, wobei die maximale Einschlussmenge als die Menge definiert ist, bis zu der die zyklischen Moleküle maximal eingeschlossen werden können, wenn das lineare Molekül die darauf aufgereihten zyklische Moleküle einschließt, und die maximale Einschlussmenge auf 1 normiert ist.
  13. Material nach einem der Ansprüche 1 bis 12, wobei das Polymer und das zyklische Molekül im Polyrotaxan durch ein Vernetzungsmittel chemisch miteinander verbunden sind.
  14. Material nach einem der Ansprüche 1 bis 13, wobei das Vernetzungsmittel ein Molekulargewicht von unter 2.000 hat.
  15. Material nach einem der Ansprüche 1 bis 14, wobei das Vernetzungsmittel unter Cyanurchlorid, Trimesoylchlorid, Terephthaloylchlorid, Epichlorhydrin, Dibrombenzol, Glutaraldehyd, Phenylendiisocyanat, Toluylendiisocyanat, Divinylsulfon, 1,1'-Carbonyldiimidazol und Alkoxysilanen ausgewählt ist.
  16. Material nach einem der Ansprüche 1 bis 15, das unter optischen Materialien, Kontaktlinsen, Biomaterialien, medizinischen Materialien, Reifenmaterialien, Auftragsmitteln und Klebstoffen ausgewählt ist.
  17. Verfahren zur Herstellung eines Materials, das ein Polyrotaxan und ein Polymer umfasst, wobei man:
    a) das Polymer und das Polyrotaxan miteinander mischt, wobei das Polyrotaxan ein zyklisches Molekül, ein lineares Molekül, das in den Kavitäten der darauf aufgereihten zyklischen Moleküle eingeschlossen ist, und Endgruppen umfasst, die zur Verhinderung der Dissoziation der zyklischen Moleküle jeweils an den Enden des linearen Moleküls angeordnet sind;
    b) zumindest einen Teil des Polymers physikalisch und/oder chemisch vernetzt; und
    c) den zumindest einen Teil des Polymers und das Polyrotaxan über das zyklische Molekül (Moleküle) miteinander verbindet, indem eine auf dem zyklischen Molekül befindliche Gruppe mit einer auf dem Rückgrat und/oder einer Seitenkette des Polymers befindlichen Gruppe verbunden wird.
  18. Verfahren nach Anspruch 17, wobei in Schritt b) zumindest ein Teil des Polymers chemisch vernetzt wird.
  19. Verfahren nach Anspruch 17 oder 18, wobei der Schritt c) nach dem Schritt b) durchgeführt wird.
  20. Verfahren nach Anspruch 17 oder 18, wobei der Schritt c) vor dem Schritt b) durchgeführt wird.
  21. Verfahren nach Anspruch 17 oder 18, wobei die Schritte b) und c) im Wesentlichen gleichzeitig durchgeführt werden.
  22. Verfahren zur Herstellung eines Materials, das ein Polyrotaxan und ein Polymer umfasst, wobei man:
    a) ein Monomer, aus dem das Polymer aufgebaut ist, und das Polyrotaxan miteinander mischt, wobei das Polyrotaxan ein zyklisches Molekül, ein lineares Molekül, das in den Kavitäten der darauf aufgereihten zyklischen Moleküle eingeschlossen ist, und Endgruppen umfasst, die zur Verhinderung der Dissoziation der zyklischen Moleküle jeweils an den Enden des linearen Moleküls angeordnet sind;
    b) das Monomer polymerisiert, um das Polymer zu erzeugen;
    c) zumindest einen Teil des Polymers physikalisch und/oder chemisch vernetzt; und
    d) den zumindest einen Teil des Polymers und das Polyrotaxan über das zyklische Molekül (Moleküle) miteinander verbindet, indem eine auf dem zyklischen Molekül befindliche Gruppe mit einer auf dem Rückgrat und/oder einer Seitenkette des Polymers befindlichen Gruppe verbunden wird.
  23. Das Verfahren nach Anspruch 22, wobei in Schritt c) zumindest ein Teil des Polymers chemisch vernetzt wird.
  24. Verfahren nach Anspruch 22 oder 23, wobei die Schritte b) und c) im Wesentlichen gleichzeitig durchgeführt werden.
  25. Verfahren nach einem der Ansprüche 22 bis 24, wobei die Schritte c) und d) im Wesentlichen gleichzeitig durchgeführt werden.
  26. Verfahren nach einem der Ansprüche 22 bis 25, wobei die Schritte b), c) und d) im Wesentlichen gleichzeitig durchgeführt werden.
  27. Verfahren nach Anspruch 22 oder 23, wobei der Schritt d) vor dem Schritt c) durchgeführt wird.
  28. Verfahren nach Anspruch 22 oder 23, wobei der Schritt d) nach dem Schritt c) durchgeführt wird.
EP05727602.4A 2004-03-31 2005-03-30 Polyrotaxan enthaltendes polymermaterial und herstellungsverfahren dafür Active EP1734066B1 (de)

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CN100489015C (zh) 2009-05-20
US7622527B2 (en) 2009-11-24
JP4482633B2 (ja) 2010-06-16
CA2562179C (en) 2013-07-23
WO2005095493A1 (ja) 2005-10-13
EP1734066A4 (de) 2009-06-03
JPWO2005095493A1 (ja) 2008-02-21
US20080097039A1 (en) 2008-04-24
KR20070000504A (ko) 2007-01-02
CA2562179A1 (en) 2005-10-13
CN1938367A (zh) 2007-03-28
KR101180169B1 (ko) 2012-09-05

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